Isomerization of hydrocarbons



ing application Serial No.

- their general use. Of

Patented Feb. 2o, 1944 A UNITED STA-'rss PATENT OFFICE 2,342,923 rsoivmnrza'rroN oF maocARBoNs Joseph In). Danforth, Chicago, lll., assgnor to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware Application February 28, 1942, Serial No. 432,749 4 claims. (o1.- 260.6835) This is a continuation-in-part of my co-pend- 373,961, filed January 10, 1941.

This invention relates to the treatment of essentially saturated hydrocarbons such as parafns or cycloparafns to effect isomerization and other conversion thereof and includes the treatment of hydrocarbon fractions of petroleum consisting essentially of parainns and naphthenes which occur in varying proportions in straight run gasolines and` naphthenes.

The invention is more particularly concerned' with isomerization processes employing granular metal halide catalysts of the Friedel-Crafts type by a particular Vmode of continuous operation which insures production of high yields of isomerized products per unit weight of metal halide catalyst. y

Isomerizing hydrocarbons and particularly paraiiin hydrocarbons to produce their more highly branched counterparts has received considerable impetus on the recognition by the petroleum industry that branched chain paraiiin hydrocarbons are considerably more reactive than the straight chain compounds and that in the case of normally liquid hydrocarbons boiling withiny the ordinary motor fuel range the antiknock values of the branched chain compounds are higher than the corresponding values of the straight chain compounds. The increase in antilknock value is particularly noticeable ln the case of the more highly branched compounds although improvements are noticed with even a mild degree c-f branching.

The catalysts most generally employed in effecting rearrangement ofthe saturated hydrocarbon molecules intothose of a more compact structure are those of the Friedel-Crafts type and most particularly aluminum chloride which isnot only suiliciently active at moderate temperatures but which is more or less available at moderate cost. Other aluminum halides such as, for example, aluminum bromide are more minum chloride but active than alutheir high cost precludes the metal halides broadly included in the so-called Friedel-Crafts group of catalysts very few have outstanding activity in hydrocarbon conversion reactions since nearly all those other than aluminum chloride" require high temperatures to eiect a given hydrocarbonl conversion and at these temperatures the isomerization reaction is not selective but is accompanied by undesirable side reactions. Among alternatively employable Friede -Craftsr catalysts may be mentioned the chlorides of zinc, zirconium and iron either alone or in admixture with aluminum chloride. The Friedel-Crafts type catalysts are usually used in granual form in hydrocarbon conversion reactions and may be deposited on or absorbed in the pores of granular supports. It is essential to the full attainment o'f the catalytic eiiectiveness of Friedel-Crafts catalysts that definite amounts of hydrogen halide be present since apparently there is very little activity in the absence of definite amounts of a hydrogen halide. These halides are denitely added as such rather than produced in situ by the actionv of water ides since this method of production gradually. consumes the meta1 halide and makes periodic replacement imperative.

Recent developments in isomerizing hydrocarbons with granular metal halide catalysts have included the use of granular metal halides in fixed beds to which hydrocarbons to be isomerized are passed continuously in admixture-with a hydrogen halide in regulated amounts followed by fractionation of the total products with separation of desired isomer fractions, rejection of un-l desirably heavy products, recycling of hydrogen halide and material capable of further efcient isomerizing treatment. The present process comprises improvements in this type of operation which make for greater yields per unit weight of catalyst and generally more eicient operation.

In one specificembodiment, the present invention comprises a process for isomerizing hydrocarbon mixtures consisting of lower boilingl and higher boiling constituents which consists in fractionati'ng a hydrocarbon mixture into said ,lower and higher boiling fractions, passing the lower boiling fractions through a bed ofgranular y metal halide to dissolve a portion thereof, combining a solution of metal halide with the'heavier hydrocarbon fractions and a hydrogen halide introducing the combined materials into a reactor containing granular relatively inert packing material, iractionating the products yfrom the reactor to produce Iixed gases comprising essentially a hydrogen halide, an isomerized product of desired boiling range and heavier fractions,"

returning said hydrogen halide to further use in the isomerization step;

In 'order to indicate more definitely the improvement process which constitutes the present invention a characteristic methodof operation Willlbe described in connection with the attached drawing which4 shows diagrammatically by the use of interconnected conventional units in genor steam on the metal half l .'taining valve 5 through a heating element G setting 1 to receive heat therefrom. The stock charged has preferably a considerable percentageof hydrocarbons boiling below about 100 F. which fractions are separated and used to dissolve metal halide catalysts. 'The arranged in a furnace preferred charging stocks are furthermore those Y of a straight run character containing minimum `amounts of oleiins and aromatics although the effect oi the latter will be minimized when lower boiling fractions are used as described since benzol, the lowest boiling aromatic is absent from such low boiling fractions.

During passage through heating element 6 the mixture of hydrocarbons is heated to a. temperature sufficient to insure its subsequent fractionation into lower and higher boiling fractions and after heating, the heated charge passes through line 8 containing valve 9 to a fractionator I0 of suitable design and capacity for effecting the desired separation. The vapors of the light fractionspass through vapor line II containing valve I2 and are condensed during passage through a condenser I3 from which the condensed liquid flows through line I4 containing valve I5 to an intermediate receiver I6 having a conventionall gas v release line I1 containing valve I8. The heavier fraction comprising the remainder of the charge passes through line I9 containing valve 20 from the bottom of fractionator I to intermediate receiver 2| which is also provided with a gas release line 22 containingvalve 23 for the removal I of Vany xed gases present incidentally at this point.

In accordance with the present linvention the light hydrocarbon fraction in receiver I6 is used to' dissolve a metal halide such as, for example, 45

aluminum chloride from a granular bed of material and thus the low boiling liquid fraction in receiver I6 is withdrawn by way of line 23 containing valve 30 to a pump 3| and discharged into line 3 2 containing valve 33 upward to a saturator 34 containing a bed of granular metal halide in central section 35. While the flow is indicated as being upward through the saturator, downflows may also be practiced. In the case of the upward ow shown there may be some mechanical carry 55 over of the metal halide as Well as the solution.

effect but usually there is no serious disadvantage inherent in this operation.

The light fraction carrying dissolved and entrained. metal halide passes through line 36 containing valve 31 and into isomerizing reactor 45 which contains a bed of granular packing material which may be definitely inert and act merely asa lter or which may possess absorbent or catalytic properties. Prior to t e admission 'of the stream of lower boiling hy ocarbons containing metal halide into reactor 45 regulated amounts of a hydrogen halide and the higher boiling fractions of the original hydrocarbon charge are introduced. Thus, a hydrogen halide may be supplied to pump 40 by way of line 38 containing a valve 39 and discharged through line 4I containing Valve 42 and thence into line 43 containing valve 44 and into line 36. Recycled hydrogen asiacaa as will be subsequently described. The higher boiling fraction of the original hydrocarbon charge is taken from receiver 2l by way yof line 24 containing valve 26 leading to pump 26 and dis charged through line 21 containing valve23 and leading into line36.

By thus avoiding contact of the heavier portions of'hydrocarbon mixture with a metal halide in the saturator, the formation of metal halidehydrocarbon addition complexes is prevented or at least minimized since in cases of straight run gasolines there is very little decomposition when low boiling paraffins such as butanes, pentanes and hexanes are contacted with metal halide such l5 as aluminum chloride, particularly in the absence of hydrogen halide such as hydrogen chloride or water'. Such low Vboiling fractions of straight run gasolines contain minimum amounts of ole- A iins and norom-atics and consequently, there is no chance for the formation of complexes of oleiins and aromatics at this point and the bed of metal halide particles remains clean for long periods of time. The process of the present invention includes an operation in which a straight run gasoline is stabilized in fractionator I0 to remove all ora portion of the butanes which it contains, and the butanes are used to dissolve the metal halide and carry it into the reactor in regulated amounts. The present process also oiers a control in that controlled amounts of lower boiling fractions may be passed through the saturator to dissolve and carry varying amounts of the metal'halide into the isomerizing reactor. The solubility of metal halides such as aluminum chloride will vary with the boiling ,range and chemical composition of low boiling hydrdcarbon fractions and the process may be operated, for example, by iirst employing a fraction with a relatively low end point and then increasing the amount of fraction passing through the saturator by taking over a fraction of higher end point.

' In reactor 45 the main reactions of isomerization are -brought about onv the total combined hydrocarbon feed after the addition of regu-A lated amounts of a hydrogen halide. The

of the hydrocarbon mixture charged may be used, and hydrogen may be added to the reaction zone if desired although means for this have not been indicated in the drawing. Entering metal. halide deposits upon the granulariilter and isomerization is effected to any desired extent. As the deposited metal halide becomes gradually contaminated by the formation of metal halide-hydrocarbon complexes, fresh meta halide is supplied by the incoming stream of light fraction so that isomerization in reactor 45 is continuous up to the -point o! complete 60 saturation of the absorbent granules with metal halide addition complexes, at which time the reactor would have to be cleaned out. The

granular contact materials which may be used in reactor 45.may comprise a number of diier- 05 ent materials such as, for example, relatively vinert substances such as Raschig rings, Berl saddles, crushed porcelain silica or` tlrebrick,

activated carbon, activated alumina, bauxite,

amounts of hydrogen halide such as hydrogen /chlride up to about 2liv mole per cent or higher k ing upon the character of the hydrocarbon materials passing through them. In lthe saturator and reactor temperatures may vary from about 50 to about 200 C. when dealing with ordinary straight run gasoline or naphtha fractions and this temperature may be maintained by heat f added by way of any of the entering materials.y Thus, the light fractions may be passed throughl the saturator at a temperature found essential for absorbing the required amounts of metal halide for insuring the desired degree of isomerization in the reactor and the remainder of the heat for the reactor supplied by heating the heavier fractions which do not pass through the saturator. The heating elements for the light and heavy fractions have been omitted from the drawing in the interest of simplicity. If desired thesaturator and reactor may be externally heated although this is usually a less dey sirablemode of operation.

' through line 55 containing valve 56 to a receiver 51 for isomerized product. The receiver has a draw line 60 containing valve 6I for the removal of isomerized material and line`58 containing valve 59 for the venting of gas accumulations. Heavy hydrocarbon materials and metal halidehydrocarbon complexes may be withdrawn from fractionator 49 through line 50 containing valve I and, if desired, the complexes may be separated and reused in further isomerization treatment along with fresh metal halide in so far as they possess sufcient catalytic activity.

Although the detail is not indicated inA the drawing the fractionating zone may'include further means for separating the hydrogen halide from the fractionator and returning it to the isomerizing zone. Thus, a portionor all of the gas separated in receiver 51 and comprising essentially hydrogen chloride or other hydrogen halides may be passed through line 62 containing valve 63 to recycling pump or compressor 64 which discharges the gas into line 55 containing valve 56 and thence to line 43.

The following data are introduced to indicate the type of results obtainable when operatingin accordance with the process of the present invention although it is not intended that the propchloride being introduced at this point. Temperature employed in the aluminum chloride supply zone is maintained at about 212 F., while the temperature in theisomerizlng reactor is maintained at 195 F. A pressure of 500 pounds per square inch is maintained on both the aluminum chloride supply zone and the reaction zone. Hydrogen chloride is introduced to the reaction zone at a rate corresponding to about 12 moles per 100 moles of gasoline charged to the plant.

The octane number (motor method) of the gasoline charge is 40 and the octane number of the gasoline produced in the process is found to be 70 by the same method of testing. There is a 95 per cent yield of product based on the liquid charge and it is found possible to treat 15 gallons of gasoline per pound of aluminum chloer scope of the invention should be limited in I exact accordance therewith.

A straight-run gasoline comprising essentially only paraffin and naphthene hydrocarbons is treated for the improvement of its antiknock properties in accordance with the process described in connection with the drawing. The ygasoline is fractionated to remove a lighter por- 'tion boiling below 100 F. and this lower-boiling fraction is used as'a carrier liquid for dissolving aluminum chloride and carrying the dissolved aluminum chloride into a reactor containing granular alumina, the remaining higher-boiling fractions of the gasoline along with hydrogen ride.

I claim -as my invention:

1. A process for treating parafilnic distillates boiling in the gasoline range which comprises separating the distillate into a light fraction boil.- ing below about F. and a heavier fraction. contacting said light fraction in liquid form with a metal halide insomerizing catalyst under conditions such as to dissolve a portion of said catalyst in the light fraction, commingling said heavier fraction and a hydrogen halidewith the.

solution of catalyst in the light fraction, passing the resultant mixture through a reaction zone containing a solid packing material and depositing catalyst from said solution onto the packing material, a'nd subjecting said fractions to isomerizlng conditions during their passage through the reaction zone.

42. A process for treating parainic distillates boiling in 'the gasoline range which comprises separating the distillate intoa light fraction boiling below about 100 F. and a heavier fraction, contacting said light fraction in liquid form with aluminum chloride under conditions such as to dissolve aluminum chloride in the light fraction, commingling said heavier fraction and hydrogen chloride with the solution 'of aluminum chloride in the light fraction, passing the resultant mixture through a reaction zone containing a solid packing material and depositing aluminum chloride from said solutionvonto the packing material, and subjecting said fractions to isomerizing conditions during their passage through the reaction zone.

3. A process for treating parailnic distillates boiling in the gasoline-range which comprises separating the distillate into a light fraction boiling below about 100 F. and a heavier fraction, passing said light fraction in liquid form through a body of solid metal halide isomerizlng catalyst under conditions such as to dissolve a portion of said catalyst in the light fraction, commingling said heavier fraction and a hydrogen halide with the solution of catalyst in the light fraction, passing th'e resultant mixture through a reaction zone containinga solid packing material and depositing catalyst from said solution onto the packing material, and subjecting said fractions to isomerizlng conditions during their passage through the reaction zone.

4. The process as defined in claim 3' further characterized in that said body comprises alumi- 

